Treatment of synthetic polymeric materials to impart dye affinity thereto



United States Patent TREATMENT OF SYNTHETIC POLYMERIC MATE- T IMPART-DYEAFFINITY THERETO Robert Meyer, Tassin-la-Demi-Lune, and Pierre AlphonseGarnier, Lyon,'France, assignors to Societe des Usines ChimiquesRhone-Poulenc No Drawing. Application March 3, 1952,

. Serial No. 274,672

Claims priority, application Great Britain March 12, 1951 Claims. c1.zen-79.3

The present invention relates to the treatment of syn-' It is an objectof the present invention to provide a method of treating such syntheticpolymeric materials so that they acquire an aflinity for acid dyestuffsand may, therefore, be dyed therewith.

According to the present invention, synthetic polymeric materials whichcontain nitrile groups, more especially polyacrylonitrile and itscopolymers, are mixed in solution with suitable organic nitrogenousbases in the presence of sulphonic acid. In the solid state, theresulting polymeric materials have an affinity for acid dyestuffs.Results of varying degree, in terms of alfinity for acid dyestufis, areobtained according to the particular reagents employed, but it is asimple matter to determine for any particular polymeric material themost suitable base to employ and the most suitable acid for use withthat base.

The invention may be applied to the various synthetic polymers orcopolymcrs which contain nitrile groups. Examples are polyacryl nitrileand copolymers thereof with such compounds as acrylamide, acrylicesters, and the like.

The organic nitrogenous bases employed in accordance with the inventionare the aliphatic and alicyclic, primary and secondary amines whichcontainnot more than carbon atoms. Examples are: diethylamine, n-butylaamine, ethylenediamine, hexamethylenediamine, decamethylenediamine andcyclohexylamine. The results qua afiinity for acid dyestuffs of thetreated polymer rapidly deteriorate with increase in the number ofcarbon atoms in saitl amine above the limit specified.

Typical examples of sulphonic acids suitable for use in carrying out theinvention are the benzene, toluene and methane sulphonic acids. Ifdesired, these acids may be used in conjunction with the inorganicsubstances of acid character disclosed in the specification of abandonedco-pending application Ser. No. 274,671, filed March 3, 1953, such aszinc chloride, boric acid and boron trifiuoride.

The organic nitrogenous base and the sulphonic acid may be employed inequimolecular proportions, in, for example, the form of a salt, but itis also possible to employ different proportions.

The amounts of acid and amine can vary within wide limits but, ingeneral, amounts of not less than 3 and not more than of the totalweight of the mixture are satisfactory. It is to be understood that inany event the quantity of amine employed is in excess of that which 2may be present as incidental impurity in the polymeric material treated.

The treatment of the synthetic polymeric material is efiected while thepolymer is in solution, a convenient solvent being dimethylformamide;The amine and the acid, or a salt thereof in the-presence or absence ofan additional amount of the same or different acid or base, are or isadded to the solution which is then heated to a temperature sufficientto obtain an adequate rate of reaction. A temperature of between 80 and150 C. is

generally satisfactory. The period of contact varies from severalminutes to several hours according to the nature of the reagents presentand the temperature employed. The optimum conditions: for eachparticular case may be readily determined by testing the dyeing afiinityof the product obtained, which can be done very simply, for

example, as follows samples of the solution are evaporated and theresultant solid is treated in a boiling aceticsulphuric acid bath forone hour with an acid dyestutf, p

such as Cyanol F. F. G., whereupon the product is washed inboiling wateruntil the washing water is colourless and the extent of'colouration ofthe product is observed.

i The Cyanoldyestuff referred to has the formula" Calls-NH SOaNa Thefollowing examples will serve to illustrate the invention. The solutionsobtained yield on evaporation solid products which fix 'acid dyestuflsunder the COHdI'.

tions hereinbefore'specified. According to the conditions under whichthe evaporation of the solution is effected, the solid products may beobtained in the form of filaments or films or the like. a

'- Example 3.5 parts of para-toluene sulphonic acid and 2.8 parts.

- Example II To'60 parts of a 16.7% dimethylformamide solutionofpolyacrylonitrile is added the following composition:

Parts Para-toluene-sulphonic acid 3.5 Hexamethylene di 2.2

The mixture is reacted for 30 minutes on a boiling water bath or for 15minutes at C.

Example III To 60 parts of a 16.7% dimethylformamide solution ofpolyacrylonitrile are added 4.4 parts of the paratoluene-sulphonic basicsalt of ethylene diamine (obtained by adding 1 mol ofpara-toluene-sulphonic acid to an Patented Dec. 11, 1956 like and whichhas substantially noafl'inity foracid, dyestuffs, to confer upon theproduct an aifinity for acid dyestuffs when in the solid state, whichmethod comprises heating said polymer in solution with a hydrocarbonsulphonic acid and: aehydrocarbon amine selected from the classconsisting of those primary and secondary aliphatic and alicyclic'aminescontaining not m'ore' than I carbon-atoms in themolecule, at least one"ofs'aid amine andsaid sulphonic. acid being, at least? partly inithe ofnq xeq l aitri erare added 515"- pans. tavern-t Henc x t .1. 4mmcyclohex am nez and-2 1c;-

991 1 @WlfifiisltlQFgQ. t Example VIP? a 1 Q- pa t i a 37 1 met iq namis;sqlufiqnz 'la it t le ai es V a r Rh n f -l13 f gdl yle n ne aa thetmixe tugre isi heated for.,1 minutesat 140 Y-Q; V i

' Example VII" tofiqiaartsr fi 1 7% e yl drmam e olu on; ofaQ copolymerofpolyacrylom'ti'ile and methyl acrylate in rqne par .qfae y a e. orparts. PQlY 'Q YI- nitrile) are' added 315 parts ofpara-toluene-sulphonic acid and 4 parts of cyclohexylamine, and themixture is heated for minutes at 140 C.

Example 7 To 60 parts of a 16.7%..dimethylformamide solution of acopolymer of polyacrylonitrile and acrylamide (containing one partoftacrylamid'et for 9 parts of polyacrylonitrile) are added 3.5 parts ofpara-toluene-sulphonic acid and 4 parts of cyclohexylamine, and themixture is heated for 15 minutes at 1405C.

Example IX Tof 7120; parts er; a 1617j%"dimethylforrnamide solution,

polyac yl n t e r ad ed 1; Par s f; iu ylamine.v

ie ianef phonat n g r part i fiprbu rl mine-y, and;

the i xt e s' eat d or, 1,5 min tcs t 1 0+ 451Z'Q weel im v 1." A methodof' treatingan; acrylonitr il'e pglymer,

rwhich material may be formed into filaments and'tli'e like and whichhas substantially-11in aflinity for acid dyestuffs, to tw f rt q hetpqdqct anafi ni x o ci res n i 1 1 d tate -:mth9c1i m; p e "I- I 1 ,rbymern lu eng i hi d'r 2"- cab-6n: pho r s i df y roc rbon mine se ec eff o'nr the classconsisting ofxth'ose primary andjsecondary aliphaticand alicyclic amines containing notzmore'than lfaibofi h f 9 r liq lflqbiflfif l nfi a of ai'nin ef and 'snlphonicj "aei d 'being;not'lessthan' 2 31% and notfgreater than 375% of the =weight oifjtlie polymer,and removing the js61ve1i; ofjtl e said, solution, to form; a slidchipdiiidnofthe said-polymer; aminef and sulg phonic acid. V 7 Q 2. Amethod of treating-t an=,,-acrylonitrile polymer, hich --m t a ma eflowed tt filaments. ndn h 1 p s]; Par luen form, of, an acid, additionsalt and the. combined. quantity of amine and sulphonic acidbeingnot;less.than 23%" and not greater than 75% of the weight of, thepolymer, and removingthesolventof"the saidso'lution to form a solidcomposition of the said polymer, amine and sulphonic acid: V a

3. A method of treating an acrylonitrile polymer, which material may beformedinto'filaments and the like and which has substantially noafiinity for acid dyestufis,

When-inthesolid-state; which methodcomprisestmixiiig; said polymer-insolution with a hydrocarbonsuiplionicj' acid and a hydrocarbon amineselected from tlie'fclastr consistingof thoseprimary and' secondaryaliphatic and alieyclicamines containing not more than 10 carbonatomsin-the moleculeand heating'the mixture in a comf mon solvent; thecombined quantity of amine and"sul'-f phonic aeid beingnot less-than 23%and notfgreaterfthalr 25 of the -weig-l1tof the polymer; andremovingdlie solvent: of the said solution to forma solid composition of4. A method of treating an acrylonitrile polymer: which- .polymer may:be formed intcrfilaments-end the like=and whieh=hassubstantially no"afiinity'for aciddye;

' stuffs; to confer' upon thesame an afiinity iirth'esolid stategtoaciddyestuffs whiclr-comprisesheating amiXtnre' ofa-the-polymer; a solventtherefor; a-hydrocarbon*amine selected LfI'Om th'eclassconsisting ofthose primaryj'an'di secondary aliahatic-= and alicycl-ie amines'containingfnof moreathan l-(l carbonatomsin' the molecule and a-liydro-"carbon :sulphonie acid-=selected f'rom*the* benzene; toluene andmethanesulphonic acids, the com'bined quantit'y of aminei and sulphonicacid being not-Jess than 23%- and;

, not greater than 75 of the weight of the polymer, 'and' removing the-solventof the said solution to"form-a-solid composition of the saidpolymer; amine-andsulphonic? acids I 5:. Aimethodi. as claimedat claimlinewhiclf 'tlie, sol? vent is dimethylformamide. 1*

UNITED"STATESTATENTS' 23168330 Kropa, Apr-2 :26, 1949.;

6 13,8 17 GreatBritain nee. 191 613;818 G'reatBritain D'ec. 3;,19486

1. A METHOD OF TREATING AN ACRYLONITRILE POLYMER, WHICH MATERIAL MAY BEFORMED INTO FILAMENTS AND THE LIKE AND WHICH HAS SUBSTANTIALLY NOAFFINITY FOR ACID DYE. STUFFS, TO CONFER UPON THE PRODUCT AN AFFINITYFOR ACID DYESTUFFS WHEN IN THE SOLID STATE, WHICH METHOD COMPRISESHEATING SAID POLYMER IN SOLUTION WITH A HYDROCARBON SULPHONIC ACID AND AHYDROCARBON AMINE SELECTED FROM THE CLASS CONSISTING OF THOSE PRIMARYAND SECONDARY ALIPHATIC AND ALICYCLIC AMINES CONTAINING NOT MORE THAN 10CARBON ATOMS IN THE MOLECULE, THE COMBINED QUANTITY OF AMINE ANDSULPHONIC ACID BEING NOT LESS THAN 23% AND NOT GREATER THAN 75% OF THEWEIGHT OF THE POLYMER, AND REMOVING THE SOLVENT OF THE SAID SOLUTION TOFORM A SOLID COMPOSITION OF THE SAID POLYMER, AMINE AND SULPHONIC ACID.